US9169571B2 - Methods for the electrolytic production of xylo-pent-1,5-diose - Google Patents

Methods for the electrolytic production of xylo-pent-1,5-diose Download PDF

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US9169571B2
US9169571B2 US13/058,121 US200913058121A US9169571B2 US 9169571 B2 US9169571 B2 US 9169571B2 US 200913058121 A US200913058121 A US 200913058121A US 9169571 B2 US9169571 B2 US 9169571B2
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glucuronic acid
solution
diose
pent
xylo
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US20110180418A1 (en
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Jonathan A. Stapley
J. David Genders
Daniel M. Atherton
Peter M. Kendall
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Dfi Usa LLC
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Dynamic Food Ingredients Corp
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    • C25B3/02—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • C25B11/063—Valve metal, e.g. titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • D-Glucuronic acid (glucose with carbon-6 oxidized to a carboxylic acid) and its derivatives are ideal candidates for such a decarboxylation.
  • Heikkila et al. in published US patent application US2003/0097029, describes the production of xylitol from sources including glucuronic acid.
  • D-glucuronic acid is used as the starting material, it is first hydrogenated to yield L-gulonic acid, which is then decarboxylated by either hypochlorous acid (Example 5) or by the Ruff Degradation (Example 6), both standard carbohydrate decarboxylation methods, to yield L-xylose.
  • hypochlorous acid Example 5
  • Ruff Degradation Example 6
  • the present disclosure provides methods and electrolytic cells for the electrolytic oxidative decarboxylation of glucuronosides to yield xylo-pent-1,5-diose.
  • preferred methods and electrolytic cells described herein use a graphite foil electrode to provide improved current efficiency and/or reaction selectivity for the electrolytic oxidative decarboxylation of glucuronosides to yield xylo-pent-1,5-diose.
  • the improved current efficiency and reaction selectivity achieved in this manner provide substantial improvements for performing the electrolytic oxidative decarboxylation of glucuronoside substrates in a more cost-effective manner.
  • the methods of producing xylo-pent-1,5-diose include the electrolytic oxidative decarboxylation of D-glucuronic acid or D-glucuronic acid glycoside.
  • the electrolytic oxidative decarboxylation step is preferably performed in an electrolytic cell using a graphite foil anode.
  • the D-glucuronic acid or D-glucuronic acid glycoside may be methyl alpha-D-glucuronopyranoside.
  • the D-glucuronic acid or D-glucuronic acid glycoside is preferably maintained in a solvent, where 35%-80% (more preferably about 50%) of the D-glucuronic acid or D-glucuronic acid glycoside is neutralized during the electrolytic decarboxylation.
  • the solvent is preferably water, although other solvents can also be used, the starting D-glucuronic acid or D-glucuronic acid glycoside may be 50% neutralized methyl alpha-D-glucuronopyranoside.
  • FIG. 1 is a reaction scheme showing the reaction step.
  • FIG. 2 is a reaction scheme showing examples of certain preferred reaction steps.
  • FIG. 3 is a schematic of an electrolytic oxidative decarboxylation step.
  • the methods for the production of xylo-pent-1,5-diose disclosed in present disclosure preferably include the step of the electrolytic oxidative decarboxylation of a D-glucuronic acid glycoside.
  • D-glucuronic acid glycoside refers to any D-glucuronic acid compound with a where the D-glucuronic acid is in a glycosidic linkage.
  • xylo-pent-1,5-diose refers to carbohydrate with chemical formula C5H805.
  • a Fischer Projection of the xylo-pent-1,5-diose structure (1) is provided below.
  • decarboxylation refers to the removal of a carboxyl group (—COOH) by a chemical reaction or physical process. Typical products of a decarboxylation reaction may include carbon dioxide (CO2) or formic acid.
  • electrochemical refers to chemical reactions that can take place at the interface of an electrical conductor (an electrode) and an ionic conductor (the electrolyte). Electrochemical reactions can create a voltage potential between two conducting materials (or two portions of a single conducting material), or can be caused by application of external voltage. In general, electrochemistry deals with situations where an oxidation and a reduction reaction is separated in space.
  • electrolytic refers to an electrochemical oxidation or reduction reaction that results in the breaking of one or more chemical bonds. Electrolytic reactions as used herein preferably describe reactions occurring as a product of interaction with a cathode or anode.
  • any concentration ranges, percentage range, or ratio range recited herein are to be understood to include concentrations, percentages or ratios of any integer within that range and fractions thereof, such as one tenth and one hundredth of an integer, unless otherwise indicated.
  • any number range recited herein relating to any physical feature, such as polymer subunits, size or thickness are to be understood to include any integer within the recited range, unless otherwise indicated.
  • the terms “a” and “an” as used above and elsewhere herein refer to “one or more” of the enumerated components.
  • a polymer refers to one polymer or a mixture comprising two or more polymers.
  • the term “about” refers to differences that are insubstantial for the relevant purpose or function.
  • derivative refers to a chemically or biologically modified version of a chemical compound that is structurally similar to a parent compound and (actually or theoretically) derivable from that parent compound.
  • a derivative may or may not have different chemical or physical properties of the parent compound.
  • the derivative may be more hydrophilic or it may have altered reactivity as compared to the parent compound.
  • Derivatization i.e., modification
  • derivative is also used to describe all solvates, for example hydrates or adducts (e.g., adducts with alcohols), active metabolites, and salts of the parent compound.
  • adducts e.g., adducts with alcohols
  • active metabolites e.g., adducts with alcohols
  • salts of the parent compound e.g., adducts with alcohols
  • the type of salt that may be prepared depends on the nature of the moieties within the compound.
  • acidic groups for example carboxylic acid groups
  • alkali metal salts or alkaline earth metal salts e.g., sodium salts, potassium salts, magnesium salts and calcium salts
  • salts quaternary ammonium ions and acid addition salts with ammonia and physiologically tolerable organic amines such as, for example, triethylamine, ethanolamine or tris-(2-hydroxyethyl)amine.
  • Basic groups can form acid addition salts, for example with inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or with organic carboxylic acids and sulfonic acids such as acetic acid, citric acid, benzoic acid, maleic acid, fumaric acid, tartaric acid, methanesulfonic acid or p-toluenesulfonic acid.
  • Compounds which simultaneously contain a basic group and an acidic group for example a carboxyl group in addition to basic nitrogen atoms, can be present as zwitterions. Salts can be obtained by customary methods known to those skilled in the art, for example by combining a compound with an inorganic or organic acid or base in a solvent or diluent, or from other salts by cation exchange or anion exchange.
  • analogue refers to a chemical compound that is structurally similar to another but differs slightly in composition (as in the replacement of one atom by an atom of a different element or in the presence of a particular functional group), but may or may not be derivable from the parent compound.
  • a “derivative” differs from an “analogue” in that a parent compound may be the starting material to generate a “derivative,” whereas the parent compound may not necessarily be used as the starting material to generate an “analogue.”
  • the step of oxidative decarboxylation of a reactant substrate is preferably performed by an electrochemical oxidative decarboxylation of the reactant substrate.
  • FIG. 1 shows a schematic diagram describing various methods related to the production of xylo-pent-1,5-diose.
  • the methods include the step of electrolytic decarboxylation of a suitable reactant to produce xylo-pent-1,5-diose.
  • the reactant can be provided as a solution of the reactant placed in contact with an electrode to effect a decarboxylation of the reactant so as to produce xylo-pent-1,5-diose.
  • Any suitable D-glucuronic acid or D-glucuronic acid glycoside capable of producing xylo-pent-1,5-diose as a product of an electrolytic decarboxylation step can be used as a reactant.
  • the reactant is preferably methyl alpha-D-glucuronpyranoside.
  • Suitable reactants include derivatives and analogs of the carboxylic acid reactant can include reactants with chemical structure variations that insubstantially vary the reactivity of the molecule from undergoing an electrolytic decarboxylation process to produce xylo-pent-1,5-diose or an intermediate that can be converted to xylo-pent-1,5-diose.
  • FIG. 1 shows an exemplary reaction scheme where D-glucuronic acid is a first reactant 10 that undergoes a decarboxylation reaction 30 to produce a xylo-pent-1,5-diose product 50 . Also shown is an alternative aspect of the first embodiment, wherein a D-glucuronic acid glycoside is a second reactant 20 that undergoes an oxidative decarboxylation reaction 40 to produce the xylo-pent-1,5-diose product 50 .
  • the decarboxylation reaction 30 , 40 is performed electrochemically.
  • electrolytic decarboxylation of a reactant in a solution provides a desired product or intermediate that can be subsequently converted to the desired product.
  • FIG. 2 shows the preferred reaction steps.
  • the reactant is methyl alpha-D-glucuronopyranoside 60.
  • the reactant can be provided in a suitable solution comprising at least the reactant and a solvent.
  • the reactant can be dissolved in the solvent by any suitable method, including stirring and/or heating where appropriate.
  • the solvent can be any aqueous solvent in which the reactant can dissolve to a desired extent.
  • the solvent is water or any water-miscible solvent-water combination.
  • solvents can comprise one or more of the following: water, methanol, ethanol, propanol, dioxane and acetonitrile.
  • the solution is preferably an acidic solution comprising a D-glucuronic acid or D-glucuronic acid, or a combination thereof.
  • the acid reactant solution can be provided with about 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100% of one or more reactant acids neutralized.
  • 10%-100% of at least one D-glucuronic acid or D-glucuronic acid glycoside reactant is neutralized. More preferably, about 35%-80% of a D-glucuronic acid or D-glucuronic acid glycoside reactant present is neutralized. Most preferably, about 50% of the D-glucuronic acid or D-glucuronic acid glycoside reactant present in a reactant acid solution is neutralized.
  • the reactant acid solution is provided at about 10-100% neutralization, more preferably about 35-80% neutralization and most preferably about 50% neutralization of the reactant acid.
  • the pH can be permitted to increase as the electrolytic reaction proceeds.
  • the pH could be provided and/or maintained within a desirable range throughout the reaction, for example by conducting the reaction in an ion exchange resin.
  • the pH could also be controlled by using a divided electrolytic cell with a cation exchange membrane.
  • the reactant acid solution can have any suitable pH to provide a desired concentration of dissociated reactant.
  • the pH is preferably between about 3.0 and 4.0 prior to beginning the decarboxylation reaction.
  • the pH is preferably between 3.0 and 4.0 prior to beginning the decarboxylation reaction.
  • the residual reactant can be recycled by separating the starting material from products, for example by use of an anionic exchange resin.
  • a partially decarboxylated solution of acid can contain both the starting acid (e.g., D-glucuronic acid or D-glucuronic acid glycoside) and the aldehydic product (e.g., xylo-pent-1,5-diose).
  • the negatively charged D-glucuronic acid or D-glucuronic acid glycoside can adhere to positively charged anionic exchange media.
  • a partially reacted solution can be passed over a bed or column of ion exchange resin beads to replace the D-glucuronate or D-glucuronate glycoside with hydroxyl moieties (OH ⁇ ).
  • the solution can then be passed over cationic resin to strip any cations and neutralize the OH—.
  • the resulting solution can comprise higher levels of the nonionic species (e.g., xylo-pent-1,5-diose).
  • the anionic exchange resin Once the anionic exchange resin is saturated with D-glucuronate or D-glucuronate glycoside, it can be removed by treating the resin with OH—. While the ion exchange resin recycling process has been illustrated with respect to hydroxyl (OH—) functional groups, other suitable groups may also be employed.
  • the electrochemical decarboxylation of a suitable acid reactant can be performed using any suitable structure.
  • the electrochemical decarboxylation is performed by contacting an acid reactant solution comprising a D-glucuronic acid or D-glucuronic acid glycoside with an anode, where the reactant can be oxidative decarboxylated.
  • an acid reactant solution comprising a D-glucuronic acid or D-glucuronic acid glycoside
  • the reactant can be oxidative decarboxylated.
  • Contact between the starting material and the anode can elicit the decarboxylation, which can result in liberation of carbon dioxide and formation of a product such as xylo-pent-1,5-diose.
  • the product of the decarboxylation is preferably an aldehyde such as xylo-pent-1,5-diose, or an intermediate such as an analog or derivative of xylo-pent-1,5-diose that can be converted to xylo-pent-1,5-diose.
  • aldehyde such as xylo-pent-1,5-diose
  • an intermediate such as an analog or derivative of xylo-pent-1,5-diose that can be converted to xylo-pent-1,5-diose.
  • the electrochemical decarboxylation of the reactant is conducted in an apparatus having any configuration comprising an anode in electrically conducting communication with a cathode.
  • FIG. 3 shows a schematic of an electrochemical apparatus for decarboxylation of a reactant acid to form a desired product, such as erythrose.
  • the apparatus comprises an anode 502 connected through a means for electrical conduction 504 to a cathode 508 .
  • the anode 502 preferably comprises a graphite foil reactive surface where oxidation of the reactant acid can occur.
  • the reactant acid 200 can be a D-glucuronic acid or D-glucuronic acid glycoside as described above that is oxidized at or near the reactant surface of the anode 502 to form a product 250 such as xylo-pent-1,5-diose.
  • the electrochemical cell further comprises a cathode 508 , where a reduction can occur within the electrochemical cell.
  • the cathode 508 can be formed from any suitable material having a desired level of electrical conductivity, such as stainless steel.
  • the decarboxylation reaction at the anode can be: methyl alpha-D-glucuronopyranoside-2 e ⁇ --->xylo-pent-1,5-diose+CO 2 +methanol
  • the counter electrode reaction can be: 2H 2 0+2 e ⁇ ----->2OH ⁇ +H 2
  • some current can be lost to the production of O 2 gas at the anode.
  • the electrolytic cell can have any suitable configuration.
  • An apparatus for the decarboxylation of a reactant substrate preferably comprises an electrochemical cell.
  • the electrochemical cell can be configured to maintain the acid solution comprising the reactants in contact with an anode (undivided configuration).
  • a cathode can be maintained in contact with the acid solution in the same cell as the anode, or in a separate, second cell (a divided configuration).
  • a means for ion transport preferably connects the first and second cell, such as a semi-permeable membrane.
  • the membrane is permeable to protons.
  • experiment 646-11 the experiments detailed in this report were performed in a glass cell using a flag anodes.
  • the glass cell consisted of a large test tube, a 5 cm 2 stainless steel cathode flag welded to a titanium rod, and a 5 cm 2 anode flag attached to a graphite rod current collector.
  • approximately 25 ml of a 1 M methyl alpha-D-glucuronoside solution (207.16 grams per liter), which was 50% neutralized with sodium hydroxide (20.00 grams per liter), was placed in the electrochemical cell.
  • Experiment 641-85 was performed with a graphite-polyimide composite anode flag formed from carbon fiber (80%) and polyimide (thermosetting variety) resin.
  • Experiment 641-125 was performed with an Electrolytica SG-202 anode flag.
  • SG-202 is a dense non-porous graphite.
  • Experiment 641-93 was performed with a 4 mm thick (PAN based) Sigratherm GFD felt anode flag.
  • Experiment 641-47 was performed with a Sigraflex 1.25 gram per cubic centimeter graphite foil anode flag.

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US13/058,121 2008-08-08 2009-07-28 Methods for the electrolytic production of xylo-pent-1,5-diose Active 2032-07-18 US9169571B2 (en)

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JP6336029B2 (ja) 2013-03-12 2018-06-06 ダイナミック フード イングリディエンツ コーポレーションＤｙｎａｍｉｃ Ｆｏｏｄ Ｉｎｇｒｅｄｉｅｎｔｓ Ｃｏｒｐ． 糖の電解脱炭酸方法
EP3559207A4 (en) 2016-12-21 2020-08-12 Creatus Biosciences Inc. XYLITOL-PRODUCING METSCHNIKOWIA SPECIES

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RU2011108378A (ru) 2012-09-27
US20110180418A1 (en) 2011-07-28
WO2010017059A3 (en) 2010-06-10
KR20110061562A (ko) 2011-06-09
EP2326749A2 (en) 2011-06-01
EP2326749A4 (en) 2012-06-27
WO2010017059A2 (en) 2010-02-11

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